JPS6015403A - Surfactant for emulsion polymerization - Google Patents
Surfactant for emulsion polymerizationInfo
- Publication number
- JPS6015403A JPS6015403A JP58123781A JP12378183A JPS6015403A JP S6015403 A JPS6015403 A JP S6015403A JP 58123781 A JP58123781 A JP 58123781A JP 12378183 A JP12378183 A JP 12378183A JP S6015403 A JPS6015403 A JP S6015403A
- Authority
- JP
- Japan
- Prior art keywords
- emulsion
- surfactant
- polymerization
- group
- emulsion polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は不飽和単量体の乳化重合用界面活性剤に関する
。更に詳しくは、エチレン性不飽和単量体又は共役ジエ
ン系、不飽和単量体、もしくはこれら単量体の混合物の
乳化重合において、表面張力が高くきわめて低泡性で、
かつ機械的安定性が良好なエマルションを提供しうる乳
化重合用界面活性剤に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a surfactant for emulsion polymerization of unsaturated monomers. More specifically, in the emulsion polymerization of ethylenically unsaturated monomers, conjugated diene-based monomers, unsaturated monomers, or mixtures of these monomers, high surface tension and extremely low foaming properties are used.
The present invention also relates to a surfactant for emulsion polymerization that can provide an emulsion with good mechanical stability.
各種高分子物質のいわゆる乳濁液であるエマルションは
塗料、繊維加工剤、接着剤、紙加工剤等として現在広く
使用されるようになっている。仁れはエマルションでは
溶媒として水を使用しているため、いわゆる溶剤型に比
し、環境汚染や人体に対する安全性の面で有利なためで
ある。しかしながら、エマルションの製造においては周
知のように重合の場を与えたり、生成エマルションの安
定化のために、一般にアルキルベンゼンスルホン酸塩、
アルキル硫酸エステル塩、高級脂肪酸塩等のアニオン界
面活性剤、ホリオキシエチレンアルキルフェニルエーテ
ル等の非イオン界面活性剤が単独あるいは混合物で原料
モノマーに対して０．１〜５重量％使用されておシ、そ
のため製造されたエマルションは発泡性が大きく、かつ
表面張力が低く、製造上あるいは使用に際して種々問題
が生じている。Emulsions, which are so-called emulsions of various polymeric substances, are now widely used as paints, fiber processing agents, adhesives, paper processing agents, and the like. This is because emulsions use water as a solvent, which is advantageous in terms of environmental pollution and safety for the human body compared to so-called solvent-based emulsions. However, in the production of emulsions, alkylbenzene sulfonates are generally used to provide a polymerization site and to stabilize the resulting emulsion.
Anionic surfactants such as alkyl sulfate salts and higher fatty acid salts, and nonionic surfactants such as holoxyethylene alkylphenyl ethers are used singly or in mixtures in an amount of 0.1 to 5% by weight based on the raw material monomer. Therefore, the emulsions produced have high foamability and low surface tension, which causes various problems in production and use.
例えば、発泡性が大きいことは、エマルション製造時に
仕込み容量が大となる、反応状態の観察が不十分となる
等の不都合をもたらす。さらに、エマルションを塗装等
に用いた場合、泡がピンホールの原因となることもある
。また、表面張力が低いとエマルションを接着剤に用い
た場合に接着力が弱くなる傾向が見られ、繊維加工剤と
して用いた場合には、エマルションの繊維に対する授透
性が太きすぎて繊維自身の特性が生かされにくくなる。For example, high foamability brings about disadvantages such as a large charging volume during emulsion production and insufficient observation of the reaction state. Furthermore, when the emulsion is used for painting, etc., bubbles may cause pinholes. In addition, when emulsions with low surface tension are used as adhesives, the adhesive strength tends to be weak, and when used as fiber processing agents, the permeability of the emulsion to the fibers is too thick and the fibers themselves characteristics become difficult to take advantage of.
さらには該活性剤は不揮撥性であるためエマルションよ
り調整された皮膜中に残存し皮膜の耐水性、密着性、引
張シ強度、耐熱性、耐候性等の低下の原因となることも
指摘されている。Furthermore, it has been pointed out that since the activator is nonvolatile, it remains in the film prepared from the emulsion and causes a decrease in the water resistance, adhesion, tensile strength, heat resistance, weather resistance, etc. of the film. has been done.
本発明者らはか７５）１現状を認識し、これらの諸問題
は理論的にはエマルション中の低分子量界面活性剤をな
くすることによシ解決することができるという方針に則
り鋭意研究の結果、炭素数６〜２２のアルキルメルカプ
タンを連鎖移動剤として用い６Ｒアミノ基含有モノマー
を必須モノマー成分としてオリゴマー化反応させた後、
酸化剤にて５級アミン基を酸化しアミンオキサイド化し
て得られる特定分子量のオリゴマーを乳化重合用界面活
性剤として用いた場合にきわめて低泡性で表面張力が高
く、かつ重合安定性および機械安定性に優れたエマルシ
ョンが調製されることを見い出し、本発明を完成させた
。The present inventors are aware of the current situation and have conducted intensive research in accordance with the policy that these problems can theoretically be solved by eliminating the low molecular weight surfactant in the emulsion. As a result, after an oligomerization reaction using an alkyl mercaptan having 6 to 22 carbon atoms as a chain transfer agent and a 6R amino group-containing monomer as an essential monomer component,
When used as a surfactant for emulsion polymerization, an oligomer with a specific molecular weight obtained by oxidizing a quintic amine group with an oxidizing agent to form an amine oxide exhibits extremely low foaming properties, high surface tension, and stable polymerization and mechanical stability. They discovered that an emulsion with excellent properties can be prepared, and completed the present invention.
即ち、本発明は連鎖移動剤として炭素数６〜２２のアル
キル・メルカプタンを用い、６級アミノ基含有モノマー
を必須モノマー成分として重合又は共重合したのち、３
Ｍ、アミン基を酸化して得られる平均分子［１，０００
〜１０，０００のアミンオキサイド基含有高分子化合物
からなる乳化重合用界面活性剤を提供するものである。That is, in the present invention, an alkyl mercaptan having 6 to 22 carbon atoms is used as a chain transfer agent, and after polymerization or copolymerization with a monomer containing a 6th class amino group as an essential monomer component, 3
M, average molecule obtained by oxidizing an amine group [1,000
The present invention provides a surfactant for emulsion polymerization comprising a polymer compound containing amine oxide groups of 10,000 to 10,000.
本発明に係る炭素数６〜２２のアルキルメルカプタンは
直鎖状であっても分岐状のものであってもよく、アルキ
ル基の原料は天然のものでも、エチレン、プロピレンの
低重合パラフィンのクラッキングなど人為的に製造され
たものでもよく、たとえばオクチルメルカプタン、ドデ
シルメルカプタン、オクタデシルメルカプタン、ヘキサ
デシルメルカプタン、テトラデシルメルカプタン等々の
メルカプタンを挙げることができる。特にオクチルメル
カプタン、ドデシルメルカプタンが好ましい。The alkyl mercaptan having 6 to 22 carbon atoms according to the present invention may be linear or branched, and the raw material for the alkyl group may be natural or cracked from low polymerized paraffin such as ethylene or propylene. Artificially produced mercaptans may also be used, and examples thereof include mercaptans such as octyl mercaptan, dodecyl mercaptan, octadecyl mercaptan, hexadecyl mercaptan, and tetradecyl mercaptan. Particularly preferred are octyl mercaptan and dodecyl mercaptan.
アルキルメルカプタンの使用量は３級アミノ基含有モノ
マーの種類や目的とする生成物の分子量によシ異なるが
通常モノマーに対し２〜２０モルチ、好ましくは５〜１
０モルチである。The amount of alkyl mercaptan to be used varies depending on the type of tertiary amino group-containing monomer and the molecular weight of the desired product, but is usually 2 to 20 molti, preferably 5 to 1 molti based on the monomer.
It is 0 morti.
本発明に係る５級アミノ基含有モノマーとしては、アク
リロイル基、メタクリロイル基、スチリル基、アリル基
又はメタリル基を有するものが好ましく、たとえば（メ
タ）アリルジメチルアミン、ジメチルアミノエチル（メ
タ）アクリレート、ジエチルアミノエチル（メタ）アク
リレート、ジメチルアミノプロピル（メタ）アクリレー
ト、ジメチルアミノエチルポリエトキシ（メタ）アクリ
レート、ジメチルアミノエチル（メタ）アクリルアミド
、ジメチルアミノプロピル（メタ）アクリルアミド、ジ
メチルアミノメチルスチレンなどが挙げられる。これら
のうち入手の容易さなεから、ジメチルアミノエチル（
メタ）アクリレート、ジエチルアミノエチル（メタ）ア
クリレート、ジメチルアミノプロピル（メタ）アクリル
アミドなどが好ましい。The monomer containing a quaternary amino group according to the present invention preferably has an acryloyl group, a methacryloyl group, a styryl group, an allyl group, or a methallyl group, such as (meth)allyldimethylamine, dimethylaminoethyl (meth)acrylate, diethylamino Examples include ethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminoethyl polyethoxy (meth)acrylate, dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, and dimethylaminomethylstyrene. Among these, dimethylaminoethyl (
Preferred are meth)acrylate, diethylaminoethyl(meth)acrylate, dimethylaminopropyl(meth)acrylamide, and the like.
本発明の５級アミノ基含有モノマーを必須構成成分とす
るオリゴマーとしては３Ｍアミノ基含有モノマー単位が
オリゴマー中に６０モルチ以上含まれるものが好ましく
、更に好ましくは５０モルチ以上含まれるものである。The oligomer containing the monomer containing a tertiary amino group of the present invention as an essential component preferably contains 60 moles or more of 3M amino group-containing monomer units, more preferably 50 mole or more.
３級アミノ基含有モノマー以外のモノマ〜としては共重
合可能ないかなるモノマ〜でもよく、例えばスチレン系
化合物、（メタ）アクリル酸（ヒドロキシ）エステル類
、ビニルアルコールの脂肪酸エステル類、（メタ）アク
リルアミド、（メタ）アクリロニトリルなどを挙げるこ
とができる。The monomer other than the tertiary amino group-containing monomer may be any copolymerizable monomer, such as styrene compounds, (meth)acrylic acid (hydroxy) esters, fatty acid esters of vinyl alcohol, (meth)acrylamide, Examples include (meth)acrylonitrile.
重合（又ｔま共重合）は溶液重合、塊状重合等いずれの
方法でも行なえるが、好ましくは低級アルコール溶媒又
は低級アルコール−水混合溶媒中で行なわれる。通常、
重合温度は４０〜１００Ｃ５好ましくは６０〜８０Ｃで
ある。必要ならば反応系中に窒素のような不活性ガスを
導入し、酸素のない雰囲気とすることができる。The polymerization (or copolymerization) can be carried out by any method such as solution polymerization or bulk polymerization, but is preferably carried out in a lower alcohol solvent or a lower alcohol-water mixed solvent. usually,
The polymerization temperature is 40-100C5, preferably 60-80C. If necessary, an inert gas such as nitrogen can be introduced into the reaction system to create an oxygen-free atmosphere.
重合反応は過酸化物、過硫酸塩又はアゾビス化合物のよ
うな公知の開始剤の存在において都合よく行なわれる。The polymerization reaction is conveniently carried out in the presence of known initiators such as peroxides, persulfates or azobis compounds.
開始剤としては例えば、過酸化水素、アゾビス−（イン
ブチロニトリル）、過硫酸カリウム、過硫酸アンモニウ
ム、過酸化ラウロイル、過酸化ｔ−ブチルなどが挙げら
れる。開始剤の量はモノマー１モル当シ０．１〜５２で
ある。Examples of the initiator include hydrogen peroxide, azobis-(imbutyronitrile), potassium persulfate, ammonium persulfate, lauroyl peroxide, and t-butyl peroxide. The amount of initiator is from 0.1 to 52% per mole of monomer.
重合後、酸化剤によ９３級アミノ基を酸化してアミンオ
キサイド化する。酸化剤としては、過酸化水素、過酢酸
、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリ
ウムなどが挙げられる。After polymerization, the 93-level amino group is oxidized with an oxidizing agent to form an amine oxide. Examples of the oxidizing agent include hydrogen peroxide, peracetic acid, ammonium persulfate, sodium persulfate, potassium persulfate, and the like.
低級アルコール系溶媒を用いて反応を行ったものは、反
応終了後、適量の水を加えトッピングによりアルコール
分を除去すれば、本発明の界面活性剤の水溶液が得られ
る。該水溶液は１０〜５０％濃度溶液として乳化重合に
供するのが便利である。When the reaction is carried out using a lower alcohol solvent, after the reaction is completed, an appropriate amount of water is added and the alcohol content is removed by topping to obtain an aqueous solution of the surfactant of the present invention. The aqueous solution is conveniently subjected to emulsion polymerization as a 10-50% strength solution.
本発明のアミンオキサイド基含有高分子化合物の分子量
が１，０００〜１０，０００の範囲にあることも重要で
ある。分子量の調整は仕込モノマー量とアルキルメルカ
プタン量との比によって行うことが出来る。アミンオキ
サイド基含有高分子化合物の分子量が１，０００未満と
なった時は生成したエマルションの起泡性が増加すると
共に表面張力も低下し、一方分子量がＩＱＯＯＯを超え
ると生成したエマルションの粘度が高くなシすぎ、取扱
いが困難となったりするので実用的ではない。It is also important that the molecular weight of the amine oxide group-containing polymer compound of the present invention is in the range of 1,000 to 10,000. The molecular weight can be adjusted by adjusting the ratio between the amount of monomers and the amount of alkyl mercaptan. When the molecular weight of the amine oxide group-containing polymer compound is less than 1,000, the foamability of the generated emulsion increases and the surface tension decreases, while when the molecular weight exceeds IQOOO, the viscosity of the generated emulsion increases. It is not practical because it is too thin and difficult to handle.
本発明の乳化重合用界面活性剤は、その親水部分にアミ
ンオキサイド基を持つものである。The surfactant for emulsion polymerization of the present invention has an amine oxide group in its hydrophilic portion.
この範時に属する界面活性剤としては、特開昭５１−２
３５３０号公報に開示されている５級アミノ基含有モノ
マーを単に重合せしめた後、アミンオキサイド化したも
のがある。しかしながらこのものは、親水基と疎水基の
バランスが十分とは言い難く、乳化重合用界面活性剤と
しての性能も十分に満足できるものとは言えない。Surfactants belonging to this category include JP-A-51-2
There is a product disclosed in Japanese Patent No. 3530 in which a monomer containing a 5th class amino group is simply polymerized and then converted into an amine oxide. However, this product cannot be said to have a sufficient balance between hydrophilic groups and hydrophobic groups, and its performance as a surfactant for emulsion polymerization cannot be said to be fully satisfactory.
しかるに、本発明の乳化重合用界面活性剤は炭素数６〜
２２のアルキルメルカプタンを連鎖移動剤として用いて
製造されている為、分子の末端に必ず疎水性基が存在す
る事となり、親水性と疎水性とのバランスが極めて適切
なものとな′シ、乳化重合における優れた乳化剤となる
。However, the surfactant for emulsion polymerization of the present invention has 6 to 6 carbon atoms.
Since it is manufactured using alkyl mercaptan No. 22 as a chain transfer agent, a hydrophobic group is always present at the end of the molecule, resulting in an extremely appropriate balance between hydrophilicity and hydrophobicity. It is an excellent emulsifier in polymerization.
本発明の乳化重合用界面活性剤を用いることによシ、モ
ノマーの乳化重合を有利に行なうことができるとともに
、得られるエマルションも優れた性能を有するものであ
る。By using the surfactant for emulsion polymerization of the present invention, emulsion polymerization of monomers can be carried out advantageously, and the resulting emulsion also has excellent performance.
本発明の乳化重合用界面活性剤を用いて行なう乳化重合
反応は公知の方法によシ行なうことができる。例えば、
モノマー１００重量部に８対し、水８０〜２００重量部
、本発明の乳化重合用界面活性剤０．５〜１０重量部、
適量の重合開始剤、さらに必要に応じて無機塩、連鎖移
動剤等を加え、窒素雰囲気下で適度な温度を設定して重
合反応を行なう。なお、ここに使用されるモノマーとし
ては、スチレン、α−メチルスチレン等の芳香族ビニル
モノマー、アクリル酸メチル、アクリル酸ブチル、メタ
クリル酸メチル等のアクリル酸又はメタクリル酸エステ
ル類、塩化ビニノペ塩化ビニリデン等のハロゲン化ビニ
ル類、酢酸ビニル等のビニルエステル類、ブタジェン、
イソプレン等の共役ジエン類を挙げることができる。こ
れらのモノマーは単独であるいは２種以上の混合物とし
て使用されてよい・次に実施例によって本発明を更に詳
しく説明するが、本発明はこれらの実施例に限定される
ものではない。なお、例中の部はすべて重量基準である
。The emulsion polymerization reaction using the surfactant for emulsion polymerization of the present invention can be carried out by a known method. for example,
8 to 100 parts by weight of monomer, 80 to 200 parts by weight of water, 0.5 to 10 parts by weight of the surfactant for emulsion polymerization of the present invention,
An appropriate amount of a polymerization initiator and, if necessary, an inorganic salt, a chain transfer agent, etc. are added, and a polymerization reaction is carried out under a nitrogen atmosphere by setting an appropriate temperature. The monomers used here include aromatic vinyl monomers such as styrene and α-methylstyrene, acrylic acid or methacrylic acid esters such as methyl acrylate, butyl acrylate, and methyl methacrylate, vinylidene chloride, vinylidene chloride, etc. vinyl halides, vinyl esters such as vinyl acetate, butadiene,
Conjugated dienes such as isoprene can be mentioned. These monomers may be used alone or as a mixture of two or more. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Note that all parts in the examples are based on weight.
くアミンオキザイドオリゴマーの合成〉（合成実施例１
〜４及び合成比較例１〜３）表−１に示す仕込原料組成
で６級アミン基含有オリゴマーを合成し、それらを過酸
化水素にて酸化することによりアミンオキサイドオリゴ
マーを得た。オリゴマーの分子量は、ポリエチレングリ
コールを標準物質と１２、ゲルパーミェーションクロマ
トグラフィーにて測定して得たものである。尚、オリゴ
マー化は仕込原料１００部に対し、イソプロピルアルコ
ール４００部、アゾビスイソブチロニトリル０．８部を
混合溶解し、窯素ガス雰囲気下７５Ｃで８時間攪拌する
ことによシ行なった。オリゴマー化反応終了後、３級ア
ミン基に対して当量の過酸化水素を加え６５、Ｃで３時
間酸化反応を行なった後、イオン交換水５００部今加え
トッピングでイソプロピルアルコール及び水を除去し、
アミンオキサイドオリゴマーを２０係水溶液として得た
。Synthesis of amine oxide oligomer (Synthesis Example 1)
4 and Synthesis Comparative Examples 1 to 3) Sixth-class amine group-containing oligomers were synthesized using the raw material compositions shown in Table 1, and amine oxide oligomers were obtained by oxidizing them with hydrogen peroxide. The molecular weight of the oligomer was determined using gel permeation chromatography using polyethylene glycol as a standard substance. The oligomerization was carried out by mixing and dissolving 400 parts of isopropyl alcohol and 0.8 parts of azobisisobutyronitrile in 100 parts of the raw materials, and stirring the mixture at 75C for 8 hours under a furnace gas atmosphere. After the completion of the oligomerization reaction, hydrogen peroxide in an amount equivalent to the tertiary amine group was added, and the oxidation reaction was carried out at C for 3 hours, followed by adding 500 parts of ion-exchanged water to remove isopropyl alcohol and water.
An amine oxide oligomer was obtained as a 20% aqueous solution.
〈エマルションの調與ソの１〉
合成実施例１〜４、合成比較例１〜３で得られた界面活
性剤及び市販のアニオン界面活性剤であるドデシルベン
ゼンスルホン酸ナトリウム、ラウリル硫酸ナトリウム、
ポリオキシエチレン（ｎ＝４ ）ノニルフェニルエーテ
ル硫酸ナトリウムを乳化重合用界面活性剤として用い、
次の方法によ勺乳化重合を行ないエマルションを調製し
た。すなわち還流冷却器、攪拌機、滴下ロート、窒素導
入管を備え九四ツロセパラプルフラスコ内に蒸留水１４
０部、乳化重合用界面活性剤１．３部、メタクリル酸１
．５部を入れアンモニア水でｐＨを４〜４．５に調製し
た後、窒素雰囲気下８０Ｃに昇温した。滴下ロートより
スチレン１５部、アクリル酸ブチル５０部、メチルメタ
クツレート３５部の混合物の１７１０量を滴下し、次い
で攪拌下過硫酸アンモニウム０．５部を含む水溶液１０
部を加えて重合反応を開始した。反応開始５分後よシ残
シのモノマー混合物を２時間かけて滴下し、さらに８０
Ｃで１時間熟成することによシエマルションを得た。ア
ンモニア水でエマル７ヨンのｐＨを８．０に調製し、該
エマルションの表面張力、起泡性、重合安定性、機械的
安定性、重合率及び粒径を測定した。その結果を表−２
に示す。<Preparation of emulsion 1> The surfactants obtained in Synthesis Examples 1 to 4 and Synthesis Comparative Examples 1 to 3 and commercially available anionic surfactants such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate,
Using polyoxyethylene (n=4) nonylphenyl ether sodium sulfate as a surfactant for emulsion polymerization,
An emulsion was prepared by carrying out emulsion polymerization according to the following method. That is, distilled water was placed in a 94-meter parallel flask equipped with a reflux condenser, a stirrer, a dropping funnel, and a nitrogen introduction tube.
0 parts, 1.3 parts of surfactant for emulsion polymerization, 1 part of methacrylic acid
．． After adjusting the pH to 4 to 4.5 with aqueous ammonia, the temperature was raised to 80C under a nitrogen atmosphere. 1,710 parts of a mixture of 15 parts of styrene, 50 parts of butyl acrylate, and 35 parts of methyl methacturate was added dropwise from the dropping funnel, and then, with stirring, 10 parts of an aqueous solution containing 0.5 parts of ammonium persulfate was added.
1 part was added to start the polymerization reaction. 5 minutes after the start of the reaction, the remaining monomer mixture was added dropwise over 2 hours, and
A sheemulsion was obtained by aging at C for 1 hour. The pH of the emulsion was adjusted to 8.0 with aqueous ammonia, and the surface tension, foaming properties, polymerization stability, mechanical stability, polymerization rate, and particle size of the emulsion were measured. Table 2 shows the results.
Shown below.
・表面張カニエマルションを蒸留水で希釈して樹脂分を
５％とし、２ＢＵにおい
てウイルヘルミイ法で測定した。- The surface tension Kanye emulsion was diluted with distilled water to make the resin content 5%, and measured at 2 BU using the Wilhelmy method.
・起泡性：樹脂分を５％濃度に希釈したエマルション１
００ｍ／を５００１ｎｌのメスシリンダーに入れ、攪拌
機
（Ｊａｐａｎ ５ｅｒｃｏ ａｎ＋、 Ｌｌ；ｄ製の型
式１ＭＴ８Ｓ１５）で５分間攪拌し、生
じた泡を含む試料の全体積を測定
し、元の試料体積に対する倍率と
して算出した。・Foaming property: Emulsion 1 with resin diluted to 5% concentration
00m/ into a 5001nl graduated cylinder, stirred for 5 minutes with a stirrer (Model 1MT8S15 manufactured by Japan 5erco an+, Ll;d), measured the total volume of the sample including the generated bubbles, and calculated it as a magnification of the original sample volume. Calculated.
・重合安定性：エマルションを１００メツシユの金網で
い過して得られた不通過分
の全ポリマーに対する重量％とし
て算出した。- Polymerization stability: The emulsion was passed through a 100-mesh wire mesh, and the weight percentage of the unfiltered fraction was calculated based on the total polymer.
ＩＩ機械的安定性；エマルションｓｏｆをマーロン法安
定度試験機を用いて１０ｋｙ／ＩＪの荷重下回転速度１
，０００ ｒｐｍで５分間攪拌した時に生じた１００メ
ツシュ金網不通過分の全ポリマー
に対する重量％として算出した。II Mechanical stability: The emulsion sof was tested at a rotational speed of 1 under a load of 10 ky/IJ using a Marlon method stability tester.
,000 rpm for 5 minutes, and the amount that passed through the 100-mesh wire gauze was calculated as the percentage by weight of the total polymer.
・重合率：エマルション固形分の対理論固形分重量％と
して算出した。- Polymerization rate: Calculated as the weight percent of the theoretical solid content of the emulsion solid content.
・粒 径：簡易濁度法にて測定した。- Particle size: Measured by simple turbidity method.
〈エマルションの調製 その２〉
乳化重合用界面活性剤として、本発明の合成実施例１の
ものと市販品であるポリオキシエチレン（ｎ＝４）ノニ
ルフェニルエーテル硫Ｈｆ ）リウム（市販品Ｃ）を用
いて、スチレン／メチルメタクリレート、スチレン／エ
チルアクリレート及びメチルメタクリレート／エチルア
クリレートの共重合反応を前述と同様の方法で行ないエ
マルションヲ得り。該エマルションの表面張力、起泡性
等を前述の方法で測定した。その結果を表−３に示す。<Preparation of emulsion Part 2> As a surfactant for emulsion polymerization, the one in Synthesis Example 1 of the present invention and the commercially available polyoxyethylene (n = 4) nonylphenyl ether sulfur Hf )lium (commercial product C) were used. The copolymerization reactions of styrene/methyl methacrylate, styrene/ethyl acrylate, and methyl methacrylate/ethyl acrylate were carried out in the same manner as described above to obtain emulsions. The surface tension, foaming properties, etc. of the emulsion were measured using the methods described above. The results are shown in Table-3.
表−２，６よシ明らかなように、合成比較例又は市販品
の中には、調製されたエマルションの機械的安定性ある
いは起泡性等の点において。As is clear from Tables 2 and 6, some of the synthetic comparative examples and commercially available products have poor mechanical stability and foaming properties of the prepared emulsions.
本発明品と同等或いはそれ以上の性能を示すものもある
が、それらは表面張力、起泡性、重合安定性、機械的安
定性のすべてを満足する訳ではない。これに対して本発
明品は、これらすべて満足し好ましい物性を有するエマ
ルションを提供することができる。Although some products exhibit performance equivalent to or better than the products of the present invention, they do not satisfy all of the requirements of surface tension, foaming properties, polymerization stability, and mechanical stability. On the other hand, the product of the present invention can provide an emulsion that satisfies all of these and has desirable physical properties.
出願人代理人 古 谷 馨Applicant's agent Kaoru Furutani
Claims (1)
プタンを用い、６Ｒアミノ基含有モノマ〜を必須モノマ
ー成分として重合又は共重合したのち、３級アミノ基を
酸化して得られる平均分子量１，０００〜１０，０００
のアミンオキサイド基含有高分子化合物からなる乳化重
合用界面活性剤。 ２５級アミノ基含有モノマーがジメチルアミノエチルメ
タクリレート、ジエチルアミノエチルメタクリレート、
ジメチルアミノエチルアクリレート、ジエチルアミノエ
チルアクリレート及びジメチルアミノプロピルメタクリ
ルアミドからなる群よシ選ばれる１種又は２種以上であ
る特許請求の範囲第１項記載の乳化重合用界面活性剤。[Scope of Claims] 1. Obtained by polymerizing or copolymerizing a 6R amino group-containing monomer as an essential monomer component using an alkyl mercaptan having 6 to 22 carbon atoms as a chain transfer agent, and then oxidizing the tertiary amino group. Average molecular weight 1,000-10,000
A surfactant for emulsion polymerization consisting of a polymer compound containing amine oxide groups. The 25th amino group-containing monomer is dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate,
The surfactant for emulsion polymerization according to claim 1, which is one or more selected from the group consisting of dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and dimethylaminopropyl methacrylamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58123781A JPS6015403A (en) | 1983-07-07 | 1983-07-07 | Surfactant for emulsion polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58123781A JPS6015403A (en) | 1983-07-07 | 1983-07-07 | Surfactant for emulsion polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6015403A true JPS6015403A (en) | 1985-01-26 |
| JPS6328441B2 JPS6328441B2 (en) | 1988-06-08 |
Family
ID=14869127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58123781A Granted JPS6015403A (en) | 1983-07-07 | 1983-07-07 | Surfactant for emulsion polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6015403A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5112509A (en) * | 1988-12-22 | 1992-05-12 | Texaco, Inc. | Non-dispersant, shear-stabilizing, and wear-inhibiting viscosity index improver |
| JP2010119949A (en) * | 2008-11-19 | 2010-06-03 | Nof Corp | Dispersant and composition |
-
1983
- 1983-07-07 JP JP58123781A patent/JPS6015403A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5112509A (en) * | 1988-12-22 | 1992-05-12 | Texaco, Inc. | Non-dispersant, shear-stabilizing, and wear-inhibiting viscosity index improver |
| JP2010119949A (en) * | 2008-11-19 | 2010-06-03 | Nof Corp | Dispersant and composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6328441B2 (en) | 1988-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ES2111673T5 (en) | POLYCARBOXYL ACIDS AS THICK AGENTS EASY TO DISPERSE. | |
| CN104610515B (en) | A kind of comb-shaped graft copolymer containing reactive group and preparation method and application | |
| JPS6012361B2 (en) | Copolymer manufacturing method | |
| JP2008527155A5 (en) | ||
| KR960014231A (en) | Fluorinated acrylic and methacrylic latises and mixtures thereof, methods for their preparation and their use in the field of hydrophobic coatings | |
| GB1577491A (en) | Preparation of copolymer emulsions of an alpha beta-unsaturated carboxylic acid and methyl acrylate | |
| JP2000355614A (en) | Carboxylated polymer composition | |
| WO1999061484A1 (en) | Aqueous emulsion and process for producing the same | |
| JP3321209B2 (en) | Method for producing cross-linked carboxyl group-containing polymer | |
| JP3732557B2 (en) | Carboxyl group-containing polymer composition | |
| JPS6015403A (en) | Surfactant for emulsion polymerization | |
| JPS5938207A (en) | Surfactant for use in emulsion polymerization | |
| KR101622803B1 (en) | Non-hydrocarbyl hydrophobically modified polycarboxylic polymers | |
| JPH05103969A (en) | High molecular surfactant | |
| JPS58152078A (en) | Novel emulsion-type pressure-sensitive adhesive | |
| JP4145735B2 (en) | Method for producing aqueous emulsion composition | |
| JP3225105B2 (en) | Method for producing core-shell type emulsion | |
| JP2804978B2 (en) | Modifier for polymer, method for producing the same, and method for modifying polymer using the same | |
| US4346190A (en) | Thickened acrylic polymer latices | |
| CN116635493A (en) | Copolymers having viscoelastic and suspension properties | |
| JPH075645B2 (en) | Surfactant for emulsion polymerization | |
| DE19610524C2 (en) | Modifier composition for polymers and process for making and using the composition | |
| CN110551249A (en) | Preparation method of high-elongation carboxyl alkyl super-concentrated emulsion polymer | |
| JPS6059243B2 (en) | Method for producing aqueous polymer emulsion | |
| KR20200046017A (en) | Alkyl-modified carboxyl group-containing copolymer, thickener comprising the copolymer, and method for preparing the copolymer |